Method of making partially carboxymethylated or phosphorylated cellulosic fibrous materials crease resistant and dye resistant



Patented Feb. 5, 1 952 s. r.

" ATED 'CELLULOSIC FIBROUS MATERIALS CREASERESISTANT AND DYE RESISTANT George G. Daul and John D. Reid, New Orleans, La.,'assignors to the United States of America asreprcsented by the Secretary of Agriculture I No Drawing. Application April 14, 1950,

Serial No. 156,032

rolaims. (o1.117-1s9.4

(Granted under the act of March 3, 1883, as

The invention herein described may be manuamended April 30, 1928; 3'70 0. G. 757) factured and used by or for'the' Government of the United States of America for governmental purposes throughout the world, without the pay- :ment to us of any royalty thereon.

This inventionv relates to textiles and has among its objects the, production of cotton textiles which are highly resistant to creasing and dyeing with ordinary direct cotton dyes." Resistance to creasing is generally obtained by the polymerization of resin forming materials in situ in the cloth. Such processes previously have beenmore successful on. rayon s'thanon cotton. It ha been postulated that thisisbecause'the more, swellable natureof the rayon allows a more thorough penetration by the, polymeric material. In our previous patent, U. S. 2,448,153, we disclosed a method of making a highly swellable cotton textile. It is among the objects of this invention to take advantage of this high swellability to obtain a more thorough penetration of the fiber with the solutions of resin-formers used;

It has generally been the practice to add acid or acid-forming materials as catalystsifor polymerization of such resins as those obtained from melamine-formaldehyde orv urea-formaldehyde."

There are objections tosuch usage; for example,

the possible degradation of the cotton when the The production of dye-resist cotton yarns and fabrics is carried'out in a number of ways. -It is known that some dye-resist properties are given to cotton when it is treated with various resins, V

for example, melamine-forr'naldehyd'e; We have also noted that the dyeing properties of the parj tially carboxymethylated cloth have been changed. For example, it will resist certain direct dyes to a moderate extent. We havenowfound that the product to be described here combines these two types of dye-resist so as togivean absolutely bleached-white appearance when attempts are made to dye it with, for example, the

direct blue dye known as Solantine Blue 4GL.

We will now describe methods by which the various-objects mentioned above may be obtained. In general, according to the invention, partially carboxymethylated cotton textiles, in the acid form, are impregnated by padding or soaking with a solution of a pre-condensate of melamineformaldehyde, urea formaldehyde,.or the like, without a catalyst. The material is then dried at a temperature below 0., then cured at temperatures ranging from 110 to 180 C. dep ending on the curing time, the higher temperatures requiring less time.

The products of the invention are crease-resistant after laundering and show. remarkable resistance to some direct cotton dyes.

The partially carboxymethylated cotton cloth used in this invention may be prepared according to the inventors patent; U. S. 2,448,153. The precondensed resin-formers, which are not intended to be a part of the patent claims, may be prepared by any of the methods known to the art, or obtained from commercial sources.

As is known to those skilled in the art, melamineor urea-formaldehyde pre-condensates will polymerize on cotton or other textiles without a catalyst but require relatively longer periods of heating which results in a tendered, almost non-usable product. The addition of an acid, or salt capable of producing an acid, asa catalyst speeds up this condensation so that a cure may be obtained in a few minutes at -150 C. A disadvantage of this in commercial practice is that the catalyst must be added to the resin-former prior to'the treatment of the textile. This results in partial condensation of the resin-former prior to impregnation, making it difiicult to get the large molecules thus produced into the innermost recesses of the fibers.

" It is among the objects of this invention to show that good impregnation of partially carboxymethylated fabric is possible with smaller resinforming molecules because it is not necessary to add a catalyst prior to impregnation. We have discovered that the acid carboxy group of carboxymcthylcellulose (CellO-CHz-COOH) strong to eifect condensation of resin within the fibers.

The products of the invention show creaseresistance and strong resistance to some cotton dyes. Cross-sections of stained samples show thorough resin penetration of individual fibers with no resin between or on the outside of fibers.

It is also among the objects of the invention to show that other cellulose derivative possessing acid groups, such as phosphorylated cellulose, or acid forming groups, for example, the ammonium salts of carboxymethylcellulose or phosphorylated cellulose, will self-catalyze resin formation in situ. The products of resin treated phosphorylated cellulose are not only crease-resistant and dye-resistant but are also flame-resistant.

The following examples illustrate the invention in greater detail:

EXAMPLE 1 One piece of plain cotton cloth (10 x "16") with a thread count of 91 x 75, a piece of mercerized cotton cloth of the same size, and, a like piece of partially carboxymethylated cotton cloth containing approximately one carboxymethyl group per 30 glucose units, were soaked in 5% acetic acid to convert the latter to the acid form, then washed in distilled water and dried. The three pieces of cloth were then airequilibrated, weighed and padded to approximately 100% pickup of a 15% solution of a commercial melamine-formaldehyde precondensate. The samples were stretched on pin frames and dried at 100 C.-for G-minutes, followed by curing at 144 C. for 6 minutes in an oven with air circulation. The samples were washed thoroughly with running water, dried, air equilibrated and weighed to determine resin pickup. Results are shown in Table 1.

EXAMPLE 2 The experiment in Example 1 was repeated to mercerized and carboxymethylated cloth treated exactly as in Example 1. Table 1.

Results are shown in 4v EXAMPLE 3 Three pieces of cotton cloth, as in Example 1 were padded with a 20% solution of urea-formaldehyde pre-condensate (methylol urea) without a catalyst, and dried and cured as in Example 1. Results are shown in Table 2.

EXAMPLE 4 Example 3 was repeated except the samples were padded with a 20% solution of methylol urea containing 5%, byweight of resin, of diammonium phosphate added as a catalyst. Results are shown in Table 2.

The above Examples 1 and 3 illustrate the eflfectiveness of partially carboxymethylated cotton. for catalysis of the condensation of resinformers of the melamine and methylol urea type. The carboxymethylated cotton becomes more creaseproo-f combined with a greater strength retention. Examples 3 and 4 are given only for comparison.

EXAMPLE 5 Five pieces of plain cotton cloth and five pieces of partially carboxymethylated cotton cloth were padded with a 15% aqueous'solution of urea-formaldehyde pro-polymer and dried for 5 minutes at C. One piece of each kind of cloth was cured for 5 minutes at 0., 0., (2.. 0;, and C. Results are shown in .Table 3. I

' EXAMPLE 6 A piece of phosphorylated cotton cloth was padded with a solution of 15% melamine formaldehyde pre-condensate and treated as in Example 1. The results were essentially the same as'with carboxymethylated cotton except the product had the added quality of being flameresistant.

Times and temperatures given in the above examples are for illustration only and are not to be considered limiting. Temperatures from l10'to C. and times from a minute or less at the higher temperatures to an hour or more at the lower limits may be used.

Not only can partially carboxymethylated fabrics be processed according to this invention, but partially carboxymethylated yarns or threads or other partially carboxymethylated cellulosic materials may also be processed.

TABLE 1 Polymerization of melamine-formaldehyde by partially carboxymethylated cotton WITHOUT ADDED. CATALYST Strength Per Cent 8 3 Net Gain g D R Retained 2 Material Per 15 ye 881st tion Per Cent ance 1 ance Cent Degrees Warp Filling Plain cott0n 15 4. 5 85 None 91. 3 98. 4 Mercerized cotton 15 5. 4 84 do i 87. 8 89. 4 carboxymethylated cotton l6 1?. 1 124 Good 85. 4 80. 4

WITH ADDED CATALYST Plain cotton 1 15 12.2 69.1 68.5 Merccrized cotton 15 13.4 63. 5 66. 4 Carboxymethylated cotton 15 16.2 86.0 79.0

1 Degrees of recovery from crease after 5 minutes (Monsanto Wrinkle Recovery Machine). The untreated controls had recoveries of 72, 60, and 72 degrees respectively.

1 All strengths are corrected to the same thread count which was 91 X75 for the plain cotton cloth.

1 Catalyst AC (Monsanto Chemical 00.).

TABLE 2 Polymerization of urea-formaldehyde by partially carboxymethylated cotton WITHOUT ADDED CATALYST I Strength Per Cent Resin N Crease et Gain Retained Material 53's.. iss- Cent Degrees Warp Filling Plain cotton 20 5.5 94 Slight 73.8 74.1 Mercerized 20 '5. 3 88 Negative.- 87. 2 88. 5 Oarboxymethyl 20 12. 4 105 Positive... 89. 5 83.

WITH ADDED CATALYST Plain cotton 20 14. 1 118 Partial. 64. 7 64. 0 Mcrcerized cotton 20 12.7 118 q- 62.5 68.8 Carboxymethyl cotton 20 8. 9 95 Positive... 91. 8 98. 9

1 Degrees of recovery from crease after minutes (Monsanto Wrinkle Recovery Machine). The

untreated controls had recoveries of 72, 60, and 72 degrees respectively.

2 Diammonium phosphate.

TABLE 3 Eflectof temperature on curing urea-formaldehyde without catalyst in plain and carbon!- methylated cotton C in Net Gain g E g Temperature Plain Oarboxy. Cotton Cotton Mm. 0. Per Cent Per Cent 5 100 1.0 7.2 5 110 2. 0 7. 7 6 120 3.1 9.2 5 130 4.9 9. 9 5 140 6.9 11.6

1 Cloth padded with 15% aqueous solution of urea-formaldehyde pro olymer. This cloth had a substitution of about 1 carboxymet yl group per 15 glucose units.

Having thus described our invention, we claim: 1. The process of making crease-resistant, dyeresistant textile material comprising impregnat- "ing partially carboxymethylated cotton with a carboxymethylated cotton with a substance that is ordinarily polymerizable to a resin in the presence of acidic catalyst, which substance is taken from the group consisting of melamine-formaldehyde pre-condensate and urea-formaldehyde precondensate, and heating to polymerize the latter in the absence of added acidic catalyst.

5. The process of making a crease-resistant. dye-resistant cellulosic fibrous textile from cellulosic fibrous textile material in which a portion of the hydrogens of the OH groups are substituted by radicals having a substituent group taken from the class consisting of free acid radicals and of such acid radicals neutralized by ammonia, which comprises: impregnating the said substituted cellulosic fibrous textile material with a polymerizable substance of the group consisting of melamine-formaldehyde and urea-formaldehyde, and heating to polymerize the substance in the absence of added acidic catalyst.

6. The process of claim 5 in which the cellulosic fibrous material is previously carboxyalkylated cotton.

7. The process of claim 5 in which the ccllulosic fibrous material is previously phosphorylated. cotton.

GEORGE C. DAUL. JOHN D. REID.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,242,218 Auer May 20, 1941 2.418525 Pollak Apr. 8, 1947 

5. THE PROCESS OF MAKING A CREASE-RESISTANT, DYE-RESISTANT CELLULOSIC FIBROUS TEXTILE FROM CELLULOSIC FIBROUS TEXTILE MATERIAL IN WHICH A PORTION OF THE HYDROGENS OF THE -OH GROUPS ARE SUBSTITUTED BY RADICALS HAVING A SUBSTITUENT GROUP TAKEN FROM THE CLASS CONSISTING OF FREE ACID RADICALS AND OF SUCH ACID RADICALS NEUTRALIZED BY AMMONIA, WHICH COMPRISES; IMPREGNATING THE SAID SUBSTITUTED CELLULOSIC FIBROUS TEXTILE MATERIAL WITH A POLYMERIZABLE SUBSTANCE OF THE GROUP CONSISTING OF MELAMINE-FORMALDEHYDE AND UREA-FORMALDEHYDE, AND HEATING TO POLYMERIZE THE SUBSTANCE IN THE ABSENCE OF ADDED ACIDIC CATALYST. 